Fuel additive systems, compositions, and methods.

ABSTRACT

In some embodiments, the present disclosure relates to fuel additives and methods for reducing a NOx produced by combusting a liquid fuel, the method comprising combining the liquid fuel and an additive, forming an enriched combustible fuel composition, wherein the additive comprises at least one compound according to Formula I, wherein R1 is selected from the group consisting of HO, EtO, PrO, BuO, i-PrO, and t-BuO; R2 is selected from the group consisting of (C═O)R3, C1-18 alkyl, C1-6 alkyl alcohol, C2-18 monounsaturated alkyl, and C1-18 polyunsaturated alkyl; and R3 is selected from the group consisting of C1-18 alkyl, C1-6 alkyl alcohol, C2-18 monounsaturated alkyl, and C1-18 polyunsaturated alkyl, wherein each stereoisomer is selected from the group consisting of E, Z, R, and S, and wherein combusting the enriched combustible fuel would produce an exhaust gas comprising from about 2% to about 98% of the NOx produced by combusting the liquid fuel alone.

FIELD OF THE DISCLOSURE

The present disclosure relates, in some embodiments, to fuel and fueladditive systems, compositions and methods.

BACKGROUND OF THE DISCLOSURE

Fuel consumption continues to grow notwithstanding volatility in globalmarket prices and known and growing concerns related to environmentalimpact.

SUMMARY

Accordingly, a need has arisen for reducing emissions produced bycombusting engine fuels by including fuel additives. The presentdisclosure relates to systems, compositions, and methods for reducingthe expense and/or environmental impact of combustion engines. Thepresent disclosure relates to a method for reducing a NOx produced bycombusting a liquid fuel, the method comprising: combining the liquidfuel and an additive to form an enriched combustible fuel composition,wherein the liquid fuel may be selected from the group consisting ofaliphatic hydrocarbons, gasoline, jet fuel, diesel, biodiesel, andcombinations thereof, wherein the additive may comprise at least onecompound according to Formula I: R₁-R₂ (I). R₁ may be selected from thegroup consisting of HO, EtO, PrO, BuO, i-PrO, and t-BuO; R₂ may beselected from the group consisting of (C═O)R₃, C₁₋₁₈ alkyl, C₁₋₆ alkylalcohol, C₂₋₁₈ monounsaturated alkyl, and C₄₋₁₈ polyunsaturated alkyl;and R₃ may be selected from the group consisting of C₁₋₁₈ alkyl, C₁₋₆alkyl alcohol, C₂₋₁₈ monounsaturated alkyl, and C₄₋₁₈ polyunsaturatedalkyl. Each stereoisomer may be selected from the group consisting of E,Z, R, S, and a combination thereof. Combusting an enriched combustiblefuel option would produce an exhaust gas may comprise from about 2% toabout 98% of the NO_(x) produced by combusting the liquid fuel alone.

A method of reducing a NOx produced by combusting a combustible fuelcomposition in a combustion engine comprising at least one combustionchamber and at least one exhaust port, the method may comprise: (a)contacting each combustion engine chamber with the combustible fuelcomposition, the combustible fuel composition may comprise: (i) a liquidfuel selected from the group consisting of aliphatic hydrocarbons,gasoline, jet fuel, diesel, biodiesel, and combinations thereof; and(ii) an additive may comprise at least one glycol having a structureaccording to Formula I: R₁-R₂ (I) wherein: R₁ may be selected from thegroup consisting of HO, EtO, PrO, BuO, i-PrO, and t-BuO; R₂ may beselected from the group consisting of (C═O)R₃, C₁₋₁₈ alkyl, C₁₋₆ alkylalcohol, C₂₋₁₈ monounsaturated alkyl, and C₄₋₁₈ polyunsaturated alkyl;and R₃ may be selected from the group consisting of C₁₋₁₈ alkyl, C₁₋₆alkyl alcohol, C₂₋₁₈ monounsaturated alkyl, and C₄₋₁₈ polyunsaturatedalkyl. Each stereoisomer may be selected from the group consisting of E,Z, R, S, and a combination thereof; (b) combusting the combustible fuelcomposition to produce an exhaust gas; and (c) venting at least aportion of the exhaust gas. An exhaust gas may comprise at an exhaustport up from about 2% to about 98% of the NO_(x) in a reference exhaustgas produced by combusting the same combustible fuel composition thatlacks the additive.

According to some embodiments, a liquid fuel may comprise at least oneof, a jet fuel, a diesel fuel, a gasoline, a naphtha, an ethanol, a coaltar, a liquefied petroleum gas, a compressed natural gas, and a butanol.A jet fuel may comprise at least one of, Avtur, aviation turbine fuel,Jet A, Jet A-1, Jct A-2, Jet A-3, Jet A-4, Jet A-5, Jct A-6, Jct A-7,Jet A-8, Jet B, Jct Propellant-4, Jet Propellant-5, Jet Propellant-7,and Jet Propellant-8. A concentration of an additive may be about 7%(w/v), by volume of an enriched combustible fuel. The method of claim22, wherein the concentration of an additive may be about 14% (w/v), byvolume of an enriched combustible fuel. A concentration of an additivemay be about 21% (w/v), by volume of an enriched combustible fuel. Aconcentration of an additive may be about 28% (w/v), by volume of anenriched combustible fuel. An exhaust gas may comprise from about 2% toabout 20% of a NO_(x) produced by combusting a liquid fuel alone. Anexhaust gas may further comprise from about 2% to about 10% of a NO_(x)produced by combusting a liquid fuel alone.

In some embodiments, an exhaust gas may further comprise from about 2%to about 5% of a NO_(x) produced by combusting a liquid fuel alone. Anexhaust gas may further comprise from about 10% to about 50% of a carbonmonoxide produced by combusting a liquid fuel alone. An exhaust gas mayfurther comprise less than about 120 ppm of carbon monoxide. An exhaustgas may further comprise less than about 60 ppm of carbon monoxide. Anexhaust gas may further comprise from about 0% to about 35% of a sulfurdioxide produced by combusting a liquid fuel alone. An exhaust gas mayfurther comprise less than about 30 ppm sulfur dioxide. An exhaust gasmay further comprise substantially no sulfur dioxide. An exhaust gas mayfurther comprise less than about 1050 ppm NO_(x). A temperature of anexhaust gas may be less than about 700° F. A temperature of an exhaustgas may be from about 85% to about 95% of a temperature produced bycombusting a liquid fuel alone. An opacity of an exhaust gas may be lessthan about 0.05%. An opacity of an exhaust gas may be less than about0.02%.

BRIEF DESCRIPTION OF THE DRAWINGS

Some embodiments of the disclosure may be understood by referring, inpart, to the present disclosure and the accompanying drawings, wherein:

FIG. 1 illustrates HPLC chromatograms of a control and a test sample,according to a specific example embodiment of the disclosure;

FIG. 2 illustrates UV-Vis spectra of a test sample according to aspecific example embodiment of the disclosure;

FIG. 3 illustrates an infrared spectrum of test sample according to aspecific example embodiment of the disclosure; and

FIG. 4 illustrates an infrared spectrum of a control specimen.

DETAILED DESCRIPTION

The present disclosure relates, in some embodiments, to systems,compositions, methods, and apparatus for reducing emissions produced bya combustion engine. Metrics for performance may include, for example,fuel efficiency, fuel consumption, engine operating temperature, and thenature and quantity of emissions. Engine performance may also beassessed in terms of engine lifespan, frequency and/or nature of repairsneeded, rough or smooth operation at idle and/or working conditions.

Incomplete combustion of engine fuel may lead to an unwanted loss inefficiency and/or cause exhaust gases to include one or more unwantedspecies. For example, engine exhaust (e.g., diesel engine exhaust) mayinclude particulates, CO, and various nitrogen oxide (NO_(x)) species,each of which or all of which may be unwanted. Accordingly, it may bedesirable to reduce, minimize, and/or prevent formation of thesematerials during combustion and/or release these materials into thesurroundings. In some embodiments, it may be desirable to reduce,minimize, and/or prevent formation of these materials during combustionby modifying a fuel composition rather than a subject combustion engine.

Fuel systems, compositions, and/or methods of the disclosure maycombust, in some embodiments, with lower emissions of total hydrocarbons(THC), non-methane hydrocarbons (NMHC), carbon monoxide (CO), carbondioxide (CO₂), oxides of nitrogen (NO_(x)), particulate matter (PM),aldehydes, ketones, alcohols, ethers, volatile- and particulate-phasepolycyclic aromatic hydrocarbons (PAH), nitrated polycyclic aromatichydrocarbons (NPAH), and/or combinations thereof.

In some embodiments, a fuel composition including a fuel additive asdisclosed herein may combust more completely than without a fueladditive. One metric of more complete combustion may be a reduction inthe volume of fuel used, for example, to achieve the same work. A fuelcomposition including a fuel additive as disclosed herein may result inat least about 4% reduction in fuel use (e.g., 4%), at least about 8%reduction in fuel use (e.g., 8%), at least about 12% reduction in fueluse (e.g., 12%), at least about 16% reduction in fuel use (e.g., 16%),at least about 20% reduction in fuel use (e.g., 20%), and/or at leastabout 24% reduction in fuel use (e.g., 24%).

According to some embodiments, a fuel composition including a fueladditive as disclosed herein may include a reduced emission uponcombustion in comparison to a corresponding fuel composition withoutsuch additive. For example, combusting a fuel composition including afuel additive may produce an exhaust gas that may comprise from about 0%to about 35% of the sulfur dioxide produced by combusting the liquidfuel alone. Combusting a fuel composition including a fuel additive mayproduce an exhaust gas that may comprise less than about 30 ppm sulfurdioxide. For example, an exhaust gas may comprise substantially nosulfur dioxide.

In some embodiments, combusting a fuel composition including a fueladditive may produce an exhaust gas that may comprise a higher opacitywhen compared to a corresponding fuel composition not containing thefuel additive. Combusting a fuel composition including a fuel additivemay produce an exhaust gas that may comprise an opacity of less thanabout 0.1%. For example, an exhaust gas produced from combusting a fuelcomposition including a fuel additive according to specific embodimentsherein, may comprise an opacity of less than about 0.05%, or of lessthan about 0.02%. Combusting a fuel composition not including a fueladditive may produce an exhaust gas that may comprise an opacity ofgreater than about 10%, or of greater than about 15%.

A fuel composition including a fuel additive as disclosed herein mayinclude a reduced emission upon combustion in comparison to acorresponding fuel composition without such additive. For example,combusting a fuel composition including a fuel additive may produce anexhaust gas that may comprise from about 10% to about 50% of the carbonmonoxide produced by combusting the liquid fuel alone. Combusting a fuelcomposition including a fuel additive may produce an exhaust gas thatmay comprise less than about 120 ppm carbon monoxide. For example, anexhaust gas may comprise less than about 90 ppm carbon monoxide, or lessthan about 60 ppm carbon monoxide, or less than about 30 ppm carbonmonoxide.

In some embodiments, a fuel composition comprising a fuel additive asdisclosed herein may have reduced emissions upon combustion incomparison to a corresponding fuel composition without the additive.Combusting a fuel composition comprising a fuel additive may produce anexhaust gas having from about 2% to about 20% of the NO_(x) produced bycombusting a corresponding fuel without the fuel additive. For example,combusting a fuel composition comprising a fuel additive may produce anexhaust gas that may comprise from about 2% to about 10% of the NO_(x)produced by combusting the liquid fuel alone, or from about 1% to about5% of the NO_(x) produced by combusting the liquid fuel alone. Anexhaust produced by combusting a fuel composition comprising a fueladditive may comprise less than about 1200 ppm NO_(R), or less thanabout 1050 ppm NO_(x), or less than about 900 ppm NO_(R).

A fuel composition including a fuel additive as disclosed herein mayinclude reduced emissions upon combustion in comparison to acorresponding fuel composition without such additive. For example,combusting a fuel composition including a fuel additive may produce anexhaust gas having a temperature that is from about 65% to about 95% ofa temperature produced by combusting the liquid fuel alone. Combusting afuel composition including a fuel additive may produce an exhaust gashaving a temperature of less than about 800° F., or of less than about700° F., or of less than about 600° F. Combustion producing an exhaustgas of a lower temperature may desirably reduce thermal air pollutionand may desirably reduce wear on combustion related parts.

In some embodiments, a combustion engine combusting a fuel compositionincluding a fuel additive may desirably provide for a reduction incarbon deposits on the combustion engine parts (e.g., fuel injectors).For example, carbon deposits may be prevented and/or removed ifpre-existing. Removal or prevention of carbon deposits may prolongengine part life.

Compositions

The present disclosure relates, in some embodiments, to a fuel additivefor reducing emissions produced by a combustion engine. Major componentsof oils (e.g., vegetable oils) and fats (e.g., animal fats) includefatty acid triglycerides. When hydrolyzed and/or transesterified, fats(e.g., animal fats) and oils (e.g., vegetable oils) may yield glycerol,monoacyl glycerol, diacyl glycerol, free fatty acids, and/or fatty acidesters (e.g., fatty acid ethyl esters). According to some embodiments, afuel additive may comprise one or more products of (partial or complete)hydrolysis of a fat (e.g., an animal fat) and/or oil (e.g., vegetableoil). In some embodiments, products of oil hydrolysis (POHs) may includeone or more fatty acids (e.g., linoleic acid, oleic acid, palmitic acid,linolenic acid, and/or stearic acid), one or more fatty acid ethylesters (e.g., linoleic acid ethyl ester, oleic acid ethyl ester,palmitic acid ethyl ester, linolenic acid ethyl ester, and/or stearicacid ethyl ester), one or more esters of a higher alcohol (e.g.,linoleic acid ethyl ester, oleic acid ethyl ester, palmitic acid ethylester, linolenic acid ethyl ester, and/or stearic acid ethyl ester), oneor more diacyl glycerols (e.g., in which the acyl groups are the same ordifferent, arranged, 1, 2- or 1, 3-, and selected from linoleic acid,oleic acid, palmitic acid, linolenic acid, and/or stearic acid), and/orone or more monoacyl glycerols (e.g., linoleoylglycerol, oleoylglycerol,palmitoylglycerol, linolenoylglycerol, and/or stearoylglycerol). In someembodiments, a POH may further include a product of oil (partial orcomplete) oxidation. Accordingly, a fuel additive may comprise, in someembodiments, one or more fatty acids (e.g., linoleic acid, oleic acid,palmitic acid, linolcnic acid, and/or stearic acid), one or more fattyacid ethyl esters (e.g., linoleic acid ethyl ester, oleic acid ethylester, palmitic acid ethyl ester, linolenic acid ethyl ester, and/orstearic acid ethyl ester), one or more esters of a higher alcohol (e.g.,linoleic acid ethyl ester, oleic acid ethyl ester, palmitic acid ethylester, linolenic acid ethyl ester, and/or stearic acid ethyl ester), oneor more diacyl glycerols (e.g., in which the acyl groups are the same ordifferent, arranged, 1, 2- or 1, 3-, and selected from linoleic acid,oleic acid, palmitic acid, linolenic acid, and/or stearic acid), and/orone or more monoacyl glycerols (e.g., linoleoylglycerol, oleoylglycerol,palmitoylglycerol, linolenoylglycerol, and/or stearoylglycerol).

An additive may include one or more products of transesterification ofan animal fat and/or vegetable oil, according to some embodiments. Uponcontact with an alcohol (e.g., ethanol), fatty acids are released fromthe glycerol radical, react with the alcohol, and may form fatty acidesters. In some embodiments, a composition may comprise a product of amodified transesterification (e.g., a partial transesterification) of atriacyl glycerol (TAG). According to some embodiments, an additivecomprising an ethyl ester (e.g., fatty acid ethyl ester) may providedesirable physical and chemical properties in comparison to acorresponding additive having a methyl ester (e.g., fatty acid methylester). For example, an additive including an ethyl ester may providedesirable miscibility with a liquid fuel across a range of temperatures,wherein the desirable miscibility may decrease viscosity. An additiveincluding an ethyl ester may provide for an increased temperaturestability in comparison to a corresponding additive having a methylester. Miscibility and stability benefits may increase as the esterlength increases from ethyl to propyl or butyl. In some embodiments, anadditive comprising a methyl ester may be weakly miscible in a liquidfuel, in comparison to a corresponding additive including an ethylester.

In some embodiments, a fuel additive may comprise a compound accordingto Formula I: R₁-R₂ (I), wherein: R₁ may be selected from the groupconsisting of HO, EtO, PrO, BuO, i-PrO, and t-BuO. R₂ may be selectedfrom the group consisting of (C═O)R₃, C₁₋₁₈ alkyl, C₁₋₆ alkyl alcohol,C₂₋₁₈ monounsaturated alkyl, and C₄₋₁₈ polyunsaturated alkyl. R₃ may beselected from the group consisting of C₁₋₁₈ alkyl, C₁₋₆ alkyl alcohol,C₂₋₁₈ monounsaturated alkyl, and C₄₋₁₈ polyunsaturated alkyl. Eachstereoisomer may be selected from the group consisting of E, Z, R, S,and a combination thereof. In some embodiments, combusting an enrichedcombustible fuel, or a fuel including a fuel additive, may produce anexhaust gas comprising from about 2% to about 98% of the NO_(x) producedby combusting the liquid fuel alone.

According to some embodiments, a fuel composition or enrichedcombustible fuel composition may comprise a fuel additive at aconcentration of about 7% (w/v) (e.g., 7% (w/v)), about 14% (w/v) (e.g.,14% (w/v)), about 21% (w/v) (e.g., 21% (w/v)), and/or about 28% (w/v)(e.g., 28% (w/v)), by volume of the fuel composition or enrichedcombustible fuel composition. A fuel composition may comprise, in someembodiments, a fuel additive at a concentration of about 0.5% to about3%, about 1% to about 5%, about 4% to about 10%, about 8% to about 15%,about 10% to about 18%, about 15% to about 23%, about 17% to about 25%,about 20% to about 30%, about 24% to about 32%, and/or about 25% toabout 35%, in each case (w/v), by volume of the fuel composition.

A liquid fuel may comprise any desired liquid fuel including, forexample, any aliphatic hydrocarbon (e.g., methane, ethane, propane,butane, pentane, hexane, heptane, octane, nonane, decane), gasoline,kerosene, jet fuel, diesel, compressed natural gas, a butanol,biodiesel, soybean oil, aviation turbine fuel, glycerol trioleate,Avtur, Propellant-4, Jet Propellant-5, Jet Propellant-7, JetPropellant-8, and/or hydroperoxides of unsaturated fatty acids, fattyacid ethyl esters, and combinations thereof. A fuel composition, forexample, may comprise soybean oil, glycerol trioleate, and/orhydroperoxides of unsaturated fatty acids. A fuel composition, forexample, may comprise fatty acid ethyl esters and ethanol. In someembodiments, a fuel composition may comprise a jet fuel and an additive.Jet fuel may comprise any desired mixture of hydrocarbons, petroleumspirits, and/or other compounds suitable for aircraft, including, forexample, fuels identified as Jet A, Jet A-1, Jet A-2, Jet A-3, Jet A-4,Jet A-5, Jet A-6, Jet A-7, Jet A-8, and/or Jet B.

A combustible fuel composition, fuel composition, or enriched fuelcomposition may comprise a liquid fuel at a concentration from about 65%(w/v) (e.g., 65% (w/v)) to about 95% (w/v) (e.g., 95% (w/v)), by volumeof the fuel composition. For example, a fuel composition may compriseabout 5% (w/v) (e.g., 5% (w/v)), about 15% (w/v) (e.g., 15% (w/v)),about 25% (w/v) (e.g., 25% (w/v)), about 35% (w/v) (e.g., 35% (w/v), 45%(w/v) (e.g., 45% (w/v)), about 55% (w/v) (e.g., 55% (w/v)), about 65%(w/v) (e.g., 65% (w/v)), about 75% (w/v) (e.g., 75% (w/v), 85% (w/v)(e.g., 85% (w/v)), and/or about 95% (w/v) (e.g., 95% (w/v)), by volumeof the fuel composition.

Methods

The present disclosure relates, in some embodiments, to operating acombustion engine. A method may comprise, for example, contacting eachcombustion engine chamber with a combustible fuel composition, thecombustible fuel composition comprising a liquid fuel (e.g., aliphatichydrocarbons, gasoline, jet fuel, diesel, and/or biodiesel) and anadditive. Operating a combustion engine with a combustible fuelcomposition comprising a fuel additive may operate with an increasedperformance and/or reduced emissions profile in comparison to operatingthe combustion engine with a corresponding fuel composition without thefuel additive. For example, including a fuel additive may increase horsepower, increase engine efficiency, reduce exhaust gas emissions, reduceengine temperature, reduce exhaust gas temperature, reduce exhaust gasopacity, and reduce fuel consumption.

A method of reducing a NOx produced by combusting a combustible fuelcomposition in a combustion engine or reducing the NOx produced bycombusting the combustible fuel composition may comprise igniting,burning, or combusting the combustible fuel composition to produce anexhaust gas. A method may include venting a portion of an exhaust gas.In some embodiments, combusting a combustible fuel comprising anadditive may produce an exhaust gas that may include, at an exhaust portup, from about 2% to about 98% of the NO_(x) in a reference exhaust gasproduced by combusting the same combustible fuel composition that lacksthe additive.

A method for reducing a NOx produced by combusting a liquid fuel maycomprise combining the liquid fuel and an additive, forming an enrichedcombustible fuel composition, wherein combusting the enrichedcombustible fuel may produce an exhaust gas comprising from about 2% toabout 98% of the NO_(x) produced by combusting the liquid fuel alone. Anadditive may comprise a compound according to Formula I R₁-R₂, whereinR₁ may be selected from the group consisting of HO, EtO, PrO, BuO,i-PrO, and t-BuO; R₂ may be selected from the group consisting of(C═O)R₃, C₁₋₁₈ alkyl, C₁₋₆ alkyl alcohol, C₂₋₁₈ monounsaturated alkyl,and C₄₋₁₈ polyunsaturated alkyl. R₃ may be selected from the groupconsisting of C₁₋₁₈ alkyl, C₁₋₆ alkyl alcohol, C₂₋₁₈ monounsaturatedalkyl, and C₄₋₁₈ polyunsaturated alkyl, wherein each stereoisomer may beselected from the group consisting of E, Z, R, and S.

According to some embodiments, combusting, igniting, and/or burning acombustible fuel having an additive as disclosed herein may reduce thevolume of fuel used, for example, to achieve the same work as combustinga fuel without the additive. Including an additive in a fuel to increasethe performance profile of a combustion engine combusting the fuel mayresult in at least about 4% reduction in fuel use (e.g., 4%), at leastabout 8% reduction in fuel use (e.g., 8%), at least about 12% reductionin fuel use (e.g., 12%), at least about 16% reduction in fuel use (e.g.,16%), at least about 20% reduction in fuel use (e.g., 20%), and/or atleast about 24% reduction in fuel use (e.g., 24%).

Combusting, igniting, and/or burning a combustible fuel having anadditive as disclosed herein may reduce a concentration of sulfurdioxide in an exhaust gas produced by combusting, igniting, and/orburning the combustible fuel having the additive. For example, a methodfor reducing the emissions made by combusting a combustible fuel byincluding an additive herein may produce an exhaust gas that maycomprise from about 0% to about 35% of the sulfur dioxide produced bycombusting the liquid fuel alone. Combusting a fuel compositionincluding a fuel additive may produce an exhaust gas that may compriseless than about 30 ppm sulfur dioxide. For example, an exhaust gas maycomprise substantially no sulfur dioxide.

In some embodiments, reducing emissions produced by combusting a fuel byincluding an additive in the fuel may include reducing the opacity of anexhaust gas produced by combusting the fuel. A fuel additive mayadditionally reduce emissions produced by combusting a fuel in acombustion engine by including the additive by reducing the opacity ofthe fuel of an exhaust gas produced by combusting the fuel. For example,an exhaust gas produced from combusting a fuel composition including afuel additive according to specific embodiments herein, may comprise anopacity of less than about 0.05%, or of less than about 0.02%.Combusting a fuel composition not including a fuel additive may producean exhaust gas that may comprise an opacity of greater than about 10%,or of greater than about 15%.

In some embodiments, an exhaust gas at the exit port of a combustionengine combusting a fuel including an additive may have a reducedconcentration of carbon monoxide in comparison to a correspondingcombustion engine combusting a fuel not including the additive. Forexample, combusting a fuel composition including a fuel additive mayproduce an exhaust gas that may comprise from about 10% to about 50% ofthe carbon monoxide produced by combusting the liquid fuel alone.Combusting a fuel composition including a fuel additive may produce anexhaust gas that may comprise less than about 120 ppm carbon monoxide.For example, an exhaust gas may comprise less than about 90 ppm carbonmonoxide, or less than about 60 ppm carbon monoxide, or less than about30 ppm carbon monoxide. Including a fuel additive as disclosed hereinmay produce an exhaust gas that may comprise from about 2% to about 20%of the NO_(R) produced by combusting a corresponding fuel without thefuel additive. For example, combusting a fuel composition comprising afuel additive and a liquid fuel may produce an exhaust gas that maycomprise from about 2% to about 10% of the NO_(R) produced by combustingthe liquid fuel alone, or from about 1% to about 5% of the NO_(R)produced by combusting the liquid fuel alone, or up to about 2% of theNO_(R) produced by combusting the liquid fuel alone. An exhaust producedby combusting a fuel composition comprising a fuel additive may compriseless than about 1200 ppm NO_(R), or less than about 1050 ppm NO_(R), orless than about 900 ppm NO_(R). According to some embodiments, anexhaust gas at the exit port may include ≤98% of the NO_(R) (e.g., NO,NO₂) in a reference exhaust gas produced by combusting the samecombustible fuel composition that lacks the additive. For example, anexhaust gas at the exit port may include ≤96%, ≤94%, ≤92%, ≤90%, ≤88%,≤86%, and/or ≤84%, of the NO_(R) in a reference exhaust gas produced bycombusting the same combustible fuel composition that lacks an additiveaccording to the present disclosure.

The operating temperature of an engine burning a combustible fuel havingan additive as disclosed in some embodiments herein may be lower than anengine burning a fuel without an additive as disclosed. For example,igniting and/or burning a combustible fuel having an additive asdisclosed in some embodiments herein may occur at a lower temperature(as assessed, for example, by the exhaust gas temperature and/or coolanttemperature) than a combustible fuel without such additive. Exhausttemperature and/or coolant temperature may be reduced by up to about 2%(e.g., 2%), by up to about 4% (e.g., 4%), by up to about 6% (e.g., 6%),by up to about 8% (e.g., 8%), by up to about 10% (e.g., 10%), by up toabout 12% (e.g., 12%), by up to about 14% (e.g., 14%), by up to about16% (e.g., 16%), and/or by more than about 16% (e.g., 16%) compared tocombustion of the same fuel without an additive as disclosed. Forexample, combusting a fuel composition including a fuel additive mayproduce an exhaust gas having a temperature that is from about 65% toabout 95% of a temperature produced by combusting the liquid fuel alone.Combusting a fuel composition including a fuel additive may produce anexhaust gas having a temperature of less than about 800° F., or of lessthan about 700° F., or of less than about 600° F. Combustion producingan exhaust gas of a lower temperature may desirably reduce thermal airpollution and may desirably reduce wear on combustion related parts.

The present disclosure relates to methods for formulating a combustiblefuel in some embodiments. A method may comprise, for example, contactinga liquid fuel (e.g., aliphatic hydrocarbons, gasoline, kerosene, jetfuel, diesel, and/or biodiesel) with an additive (e.g., one or morePOHs). According to some embodiments, formulating a combustible fuel mayrequire few or no additional measures to arrive at a desirableformulation. For example, mixing may be optional and/or predissolutionmay be unnecessary.

As will be understood by those skilled in the art who have the benefitof the instant disclosure, other equivalent or alternative compositions,devices, methods, and systems for reducing emissions produced bycombusting a liquid fuel in a combustion engine can be envisionedwithout departing from the description contained herein. Accordingly,the manner of carrying out the disclosure as shown and described is tobe construed as illustrative only.

Persons skilled in the art may make various changes in the kind, number,and/or concentration of additives without departing from the scope ofthe instant disclosure. Each disclosed method and method step may beperformed in association with any other disclosed method or method stepand in any order according to some embodiments. Where the verb “may”appears, it is intended to convey an optional and/or permissivecondition, but its use is not intended to suggest any lack ofoperability unless otherwise indicated. Persons skilled in the art maymake various changes in methods of preparing and using a composition,device, and/or system of the disclosure. Elements, compositions,devices, systems, methods, and method steps not recited may be includedor excluded as desired or required.

Also, where ranges have been provided, the disclosed endpoints may betreated as exact and/or approximations as desired or demanded by theparticular embodiment. Where the endpoints are approximate, the degreeof flexibility may vary in proportion to the order of magnitude of therange. For example, on one hand, a range endpoint of about 50 in thecontext of a range of about 5 to about 50 may include 50.5, but not 52.5or 55 and, on the other hand, a range endpoint of about 50 in thecontext of a range of about 0.5 to about 50 may include 55, but not 60or 75. In addition, it may be desirable, in some embodiments, to mix andmatch range endpoints. Also, in some embodiments, each figure disclosed(e.g., in one or more of the examples, tables, and/or drawings) may formthe basis of a range (e.g., depicted value+/− about 10%, depictedvalue+/− about 50%, depicted value+/− about 100%) and/or a rangeendpoint. With respect to the former, a value of 50 depicted in anexample, table, and/or drawing may form the basis of a range of, forexample, about 45 to about 55, about 25 to about 100, and/or about 0 toabout 100. Disclosed percentages are weight percentages except whereindicated otherwise.

All or a portion of a device and/or system for reducing an emissionproduced by combusting a liquid fuel in a combustion engine may beconfigured and arranged to be disposable, serviceable, interchangeable,and/or replaceable. These equivalents and alternatives along withobvious changes and modifications are intended to be included within thescope of the present disclosure. Accordingly, the foregoing disclosureis intended to be illustrative, but not limiting, of the scope of thedisclosure as illustrated by the appended claims.

The title, abstract, background, and headings are provided in compliancewith regulations and/or for the convenience of the reader. They includeno admissions as to the scope and content of prior art and nolimitations applicable to all disclosed embodiments.

EXAMPLES

Some specific example embodiments of the disclosure may be illustratedby one or more of the examples provided herein.

Example 1: Mass Spectrometry

The exact mass spectrometer was a KRATOS MS25 using electron impact (EI)mode. The EI source was heated to 200° C. and the electron energy wasset to 28 eV. The sample was introduced by heated probe directly intothe EI source. The sample was inserted into the probe tip and the probewith the sample was inserted through a vacuum lock into the EI source.Then the temperature of the probe tip was ramped to evaporate the sampleinto the source where EI ionization takes place. Poorly volatile orthermally labile samples do not survive this process well and oftendecompose before evaporating.

Electron impact mass spectral measurement of the neat biodiesel datashowed what looked like decomposition mass spectra indicating that thesample was decomposing before it came off the probe. The sample didn'tappear to contain volatile compounds that were thermally stable enoughto evaporate from the probe intact. None of this data is included here.

Example 2: High Performance Liquid Chromatography

High performance liquid chromatography (HPLC) was performed using aBeckman model 126 pumping unit and a Beckman 166 UV detector. The columnwas a Higgins PHALANX; C18, 150 mm×4.6 mm, 5 μm, 100 Å with detection at230 nm. Phase A was methanol and phase B was 56% isopropanol/44% hexane(v/v). The HPLC was set to run 100% phase A for 1 minute, ramp to 50%A/50% B over 15 minutes, hold at 50% A/50% B for 10 minutes, and rampback to 100% phase A in 2 minutes.

The chromatogram of sample 1 (fuel with test additive, 1% v/v inacetonitrile) is shown by the heavy line in FIG. 1. The test additive insample 1 comprised fatty acid esters. The chromatogram of sample 2(commercial grape seed oil, 1% v/v in 56% iPrOH: 44% hexane) is shown bythe thin line in FIG. 1.

The retention profile data are shown in Table 1, from which it can beseen that the combined area under the peaks eluting before 7 min is 93%of the total area, only 3% remains as DAG.

TABLE 1 Retention Time Area Area Percent 1.083 22466 0.504 93% 1.70878900 1.770 2.217 801016 17.969 2.933 2345845 52.624 3.417 219319 4.9203.708 447641 10.042 4.500 149635 3.357 5.308 50902 1.142 5.525 139800.314 6.258 13367 0.300 11.533 95657 2.146  7% 11.917 131383 2.94712.250 71648 1.607 12.625 16006 0.359 Totals 4457765 100.000

Two groups of peaks are evident in the grape seed oil chromatogram inFIG. 1 (thin line): triacyl glycerols (TAG's) near 20 minutes and diacylglycerols around 14 minutes. Fatty acid ethyl esters (FAEEs) andmonoacyl glycerols (MAGs) should not generally be present in commercialoil samples and are not seen here. The results with grape seed oil showthat the HPLC method and column used were able to separate compounds ofthese different groups.

From the thick line in FIG. 1, it appears that the test additive has noTAG, some DAG around 12 minutes, some small FAEE peaks, at least onelarge MAG peak at 2.9 min, and maybe some small early eluting free fattyacid peaks. The large peak at 2.9 min is unlikely to be a FAEE for 2reasons. First, its retention time is much earlier than is indicatedfrom the reference chromatograms for FAEEs. Second, it is 50% of thetotal peak area, i.e. 50% of the total sample. If that much FAEE waspresent in the neat sample, then it should have shown itself as anintact compound at relatively low probe temperature when the electronimpact mass spectrum was measured on the MS25 in Example 1. However,there was no clear evidence of an intact, distinct compound evaporatingoff of the heated probe.

The large peak in the HPLC chromatogram is about 50% of the total peakarea. If this were due to straight forward transesterfication of atriacylglcerol (TAG), peaks of ethyl esters (FAEES) of the other 2 fattyacids liberated in that reaction should be visible. Since glycerolprobably contributes little to the UV/vis spectra, the FAEE peaks shouldbe at least comparable in size to the MAG peak. This is not the case;the next largest peak is less than 20% of the total.

The HPLC data was collected at 230 nm because this corresponded to astrong peak in the UV-vis spectra of a test additive (FIG. 2). Sincehydroperoxides of unsaturated fatty acids may display absorbance at ornear 230 nm, tested compositions may include one or more fatty acidoxidation products.

Example 3: Infrared Spectroscopy

Infrared spectroscopy was performed using an Agilent Cary 630spectrometer equipped with a single pass diamond ATR (Attenuated TotalReflectance) accessory. Droplets of neat material were placed on thesample holder and directly analyzed.

The spectrum of sample 1 (fuel with test additive) is shown in FIG. 3and the spectrum of sample 2 (commercial grape seed oil) is shown inFIG. 4. The appearance of certain peaks (e.g., 1736 and 1743) isconsistent with the presence of products of oil hydrolysis.

1. A method for reducing a NOx produced by combusting a liquid fuel, themethod comprising: combining the liquid fuel and an additive to form anenriched combustible fuel composition, wherein the liquid fuel isselected from the group consisting of aliphatic hydrocarbons, gasoline,jet fuel, diesel, biodiesel, and combinations thereof, wherein theadditive comprises at least one compound according to Formula I:R₁-R₂  (I) wherein: R₁ is selected from the group consisting of HO, EtO,PrO, BuO, i-PrO, and t-BuO; R₂ is (C═O)R₃; and R₃ is selected from thegroup consisting of C₁₋₁₈ alkyl, C₁₋₆ alkyl alcohol, C₂₋₁₈monounsaturated alkyl, and C₄₋₁₈ polyunsaturated alkyl, wherein eachstereoisomer is selected from the group consisting of E, Z, R, S, and acombination thereof, wherein combusting the enriched combustible fuelproduces an exhaust gas comprising from about 2% to about 98% of the NOxproduced by combusting the liquid fuel alone, wherein the liquid fuelcomprises at least one of a jet fuel, a diesel fuel, a gasoline, anaphtha, an ethanol, a coal tar, a liquefied petroleum gas, a compressednatural gas, and a butanol, and wherein the jet fuel comprises at leastone of aviation turbine fuel, Jet A, Jet A-1, Jet A-2, Jet A-3, Jet A-4,Jet A-5, Jet A-6, Jet A-7, Jet A-8, Jet B, Jet Propellant-4, JetPropellant-5, Jet Propellant-7, and Jet Propellant-8.
 2. The method ofclaim 1, wherein the concentration of the additive is (a) about 7%(w/v), by volume of the enriched combustible fuel, (b) about 14% (w/v),by volume of the enriched combustible fuel, (c) about 21% (w/v), byvolume of the enriched combustible fuel, or (d) about 28% (w/v), byvolume of the enriched combustible fuel.
 3. The method of claim 1,wherein the exhaust gas comprises (a) from about 2% to about 20% of theNOx produced by combusting the liquid fuel alone, (b) from about 2% toabout 10% of the NOx produced by combusting the liquid fuel alone, or(c) from about 2% to about 5% of the NOx produced by combusting theliquid fuel alone.
 4. The method of claim 1, wherein the exhaust gasfurther comprises less than about 1050 ppm NOx.
 5. The method of claim1, wherein the exhaust gas further comprises from about 10% to about 50%of the carbon monoxide produced by combusting the liquid fuel alone. 6.The method of claim 1, wherein the exhaust gas further comprises lessthan about 120 ppm of carbon monoxide.
 7. The method of claim 1, whereinthe exhaust gas further comprises from about 0% to about 35% of thesulfur dioxide produced by combusting the liquid fuel alone.
 8. Themethod of claim 1, wherein the exhaust gas further comprises less thanabout 30 ppm sulfur dioxide.
 9. The method of claim 1, wherein atemperature of the exhaust gas is less than about 700° F.
 10. The methodof claim 1, wherein a temperature of the exhaust gas is from about 85%to about 95% of a temperature produced by combusting the liquid fuelalone.
 11. The method of claim 1, wherein an opacity of the exhaust gasis less than about 0.05%.
 12. A method of reducing a NOx produced bycombusting a combustible fuel composition in a combustion enginecomprising at least one combustion chamber and at least one exhaustport, the method comprising: (a) contacting each combustion enginechamber with the combustible fuel composition, the combustible fuelcomposition comprising: (i) a liquid fuel selected from the groupconsisting of aliphatic hydrocarbons, gasoline, jet fuel, diesel,biodiesel, and combinations thereof; and (ii) an additive comprising atleast one compound having a structure according to Formula I:R₁-R₂  (I) wherein: R₁ is selected from the group consisting of HO, EtO,PrO, BuO, i-PrO, and t-BuO; R₂ is (C═O)R₃; and R₃ is selected from thegroup consisting of C₁₋₁₈ alkyl, C₁₋₆ alkyl alcohol, C₂₋₁₈monounsaturated alkyl, and C₄₋₁₈ polyunsaturated alkyl, wherein eachstereoisomer is selected from the group consisting of E, Z, R, S, and acombination thereof, wherein the liquid fuel comprises at least one of ajet fuel, a diesel fuel, a gasoline, a naphtha, an ethanol, a coal tar,a liquefied petroleum gas, a compressed natural gas, and a butanol, andwherein the jet fuel comprises at least one of aviation turbine fuel,Jet A, Jet A-1, Jet A-2, Jet A-3, Jet A-4, Jet A-5, Jet A-6, Jet A-7,Jet A-8, Jet B, Jet Propellant-4, Jet Propellant-5, Jet Propellant-7,and Jet Propellant-8, (b) combusting the combustible fuel composition toproduce an exhaust gas; and (c) venting at least a portion of theexhaust gas, wherein the exhaust gas includes at the exhaust port upfrom about 2% to about 98% of the NOx in a reference exhaust gasproduced by combusting the same combustible fuel composition that lacksthe additive.
 13. The method of claim 12, wherein the concentration ofthe additive is (a) about 7% (w/v), by volume of the enrichedcombustible fuel, (b) about 14% (w/v), by volume of the enrichedcombustible fuel, (c) about 21% (w/v), by volume of the enrichedcombustible fuel, or (d) about 28% (w/v), by volume of the enrichedcombustible fuel.
 14. The method of claim 12, wherein the exhaust gascomprises (a) from about 2% to about 20% of the NOx produced bycombusting the liquid fuel alone, (b) from about 2% to about 10% of theNOx produced by combusting the liquid fuel alone, or (c) from about 2%to about 5% of the NOx produced by combusting the liquid fuel alone. 15.The method of claim 12, wherein the exhaust gas further comprises lessthan about 1050 ppm NOx. of carbon monoxide.
 16. The method of claim 12,wherein the exhaust gas further comprises from about 10% to about 50% ofthe carbon monoxide produced by combusting the liquid fuel alone. 17.The method of claim 12, wherein the exhaust gas further comprises lessthan about 120 ppm of carbon monoxide.
 18. The method of claim 12,wherein the exhaust gas further comprises from about 0% to about 35% ofthe sulfur dioxide produced by combusting the liquid fuel alone.
 19. Themethod of claim 12, wherein the exhaust gas further comprises less thanabout 30 ppm sulfur dioxide.
 20. The method of claim 12, wherein atemperature of the exhaust gas is less than about 700° F.
 21. The methodof claim 12, wherein a temperature of the exhaust gas is from about 85%to about 95% of a temperature produced by combusting the liquid fuelalone.
 22. The method of claim 12, wherein an opacity of the exhaust gasis less than about 0.05%.